JP2020510306A - Electronic semiconductor device, method of manufacturing electronic semiconductor device, and compound - Google Patents

Abstract

The present invention includes at least one first semiconductor layer between a first electrode and a second electrode, and the first semiconductor layer comprises (i) at least one first semiconductor layer composed of a covalently bonded atom. A hole transport matrix compound, and (ii) at least one electrical p-dopant selected from borate metal salt complexes, said borate metal salt complex comprising at least one metal cation and at least one anion. A ligand, the anionic ligand comprises an electrical p-dopant comprising at least 6 covalently bonded atoms including at least one boron atom, the first semiconductor layer comprising hole injection The present invention relates to an electronic device that is a layer, a hole injection part of a charge generation layer, or a hole transport layer, a method for manufacturing the electronic device, and a metal borate compound of each.

Description

  The present disclosure relates to an electronic semiconductor device including a non-oxidizing p-dopant in a hole injection layer and / or a hole transport layer, a method of manufacturing an electronic semiconductor device, and a compound.

  A wide range of state-of-the-art electronic devices that already utilize organic semiconductor materials require that seemingly similar devices perform similar functions such as hole injection and / or hole transport. Very different requirements are often set for certain classes of materials. As a more specific example, for example, an OLED may function as an unstructured, single OLED for illumination, or as one pixel of a complex display device including multiple OLED pixels. In some cases, the definition of a suitable material for the hole transport layer can vary significantly. Meeting such various requirements using only one structural class of material can be very difficult from a chemical point of view. This fact raises the need to study and develop many structurally different classes of materials in parallel, and in such circumstances, not only economically, but also technically and scientifically, Is a difficult task. Thus, in a wide range of various specific applications, any class of material with high versatility can be very useful.

In some cases, even in materials included in one and the same device, contradictory requirements may be imposed on materials having a particular function. A typical example is an active matrix OLED display (AMOLED). In active OLED displays comprising a plurality of OLED pixels sharing a common hole transport layer, the semiconductor material used for the layer located between the anode and the light-emitting layer and shared by the pixels is difficult. Requirements are imposed. On the one hand, the material must allow individual driving of individual pixels at the lowest possible operating voltage. On the other hand, so-called electrical crosstalk between adjacent pixels should be avoided. WO 2016/050834, which is incorporated herein by reference, states that these conflicting requirements are 1 × 10 ⁻³ S · m ⁻¹ and 1 × 10 ⁻⁸ S · m ⁻¹ , most preferably 1 × 10 ⁻ It teaches that it can be filled by a p-doped layer having a conductivity between ⁵ S · m ⁻¹ and 1 × 10 ⁻⁶ S · m ⁻¹ . Such low-conductivity p-doped hole transport layers use conventional state-of-the-art redox dopants, such as strong electron-accepting radialene compounds, in matrices that are not sufficiently doped in terms of deep HOMO levels. Can be achieved. However, there is still a need for p-dopants that meet these criteria while improving other parameters, for example, in terms of processability and device stability.

  WO 2013/052096 A1 discloses a method for doping hole injection and hole transport layers and its use in organic electronic devices such as OLEDs.

  Nuria et al. Dalton Transactions, 2014, 43, 10114-10119 discloses highly fluorinated calcium hydrotris (indazolyl) borate complexes, the structure and reactivity of which are reported.

  It is an object of the present invention to provide a wide variety of different, including electrically p-doped hole injection layers and / or electrically p-doped hole transport layers based on one broad class of p-dopants. The purpose is to provide state-of-the-art electronic devices.

  Yet another object is to provide certain compounds within the broad class of p-dopants that have high versatility when used in devices. Various devices include simple devices, as well as improved active OLED displays. In one aspect, the performance of a simple device containing a new p-dopant is sufficiently comparable or better than a similar simple device containing a state-of-the-art p-dopant. In another aspect, the new p-dopants overcome some of the shortcomings of modern dopants in complex devices such as AMOLED displays. In one aspect, electrical crosstalk between adjacent pixels of an active OLED display is reduced. In another aspect, high performance in individual OLED pixels of simple devices as well as complex display devices. In another aspect, the improved materials improve the robustness of the device by improving the stability of the device during any process step, including, for example, processing the device or certain layers of the device at elevated temperatures. Enable manufacturing.

The purpose is
Including at least one first hole transport layer between the first electrode and the second electrode;
The first hole transport layer,
(I) at least one first hole transport matrix compound comprising a covalent bond atom, and (ii) at least one electric p-dopant selected from a metal borate complex, wherein the metal borate salt An electrical p-dopant comprising at least one metal cation and at least one anionic ligand, said anionic ligand consisting of at least six covalently bonded atoms including at least one boron atom;
Including
This is achieved by an electronic device in which the first semiconductor layer is a hole injection layer, a hole injection part of a charge generation layer, or a hole transport layer.

  In one embodiment, in the metal borate complex, it may be excluded that the metal is silver (Ag).

In one embodiment, the electronic device further comprises at least one light emitting layer or at least one light absorbing layer between the first electrode and the second electrode;
The first electrode is an anode,
The first semiconductor layer is disposed between the anode and the light emitting layer or between the anode and the light absorbing layer.

  In one embodiment, the first semiconductor layer is adjacent to the anode.

  In one embodiment, said anionic ligand is at least 7, preferably at least 8, more preferably at least 9, even more preferably at least 10, even more preferably at least 11, most preferably at least 12 Consisting of a covalent bond atom.

  A covalent bond is to be understood as any binding interaction involving electron density sharing between two evaluated atoms. Here, the binding is stronger than the van der Waals dispersion interaction, and for convenience, a binding energy of 10 kJ / mol can be regarded as an arbitrary lower limit. In this sense, the term “bond” also includes coordination bonds or hydrogen bonds. However, anions and / or anionic ligands containing hydrogen bonds are not particularly preferred.

  In one embodiment, the anionic ligand is an alkyl halide, (hetero) aryl halide, (hetero) arylalkyl halide, alkylsulfonyl halide, (hetero) arylsulfonyl halide, (hetero) aryl halide It contains at least one electron withdrawing group selected from alkylsulfonyl and cyano. For brevity, (hetero) aryl halide means "aryl halide or heteroaryl halide" and (hetero) arylalkyl halide means "heteroarylalkyl or arylalkyl halide". And (hetero) arylsulfonyl halide mean "heteroarylsulfonyl halide or arylsulfonyl halide", and (hetero) arylalkylsulfonyl halide mean "heteroarylalkylsulfonyl or arylalkylsulfonyl halide" Please understand that.

  In one embodiment, the electron withdrawing group is a per-halogenated group. The term "halogenated" is to be understood as meaning that at least one hydrogen atom of the group comprising terminal hydrogen atoms or internal hydrogen atoms has been replaced by an atom selected from F, Cl, Br and I. . Further, it should be understood that in the perhalogenated group, all hydrogen atoms contained in the unsubstituted group have been replaced by atoms independently selected from F, Cl, Br and I. Thus, under a perfluorinated group, all halogen atoms replacing a hydrogen atom should be understood to be fluorine atoms.

  In one embodiment, the metal borate complex included in the electrical device has the formula (I):

Wherein M is a metal ion;
A ¹ -A ⁴ are each independently selected from the following (i) to (x);
(I) H,
(Ii) F,
(Iii) CN,
_{(Iv) C} 6 ~C ₆₀ aryl,
_{(V) C} 7 ~C ₆₀ arylalkyl,
_{(Vi) C} 1 ~C ₆₀ alkyl,
_{(Vii) C} 2 ~C ₆₀ alkenyl,
_(Viii) C _{2 ~ 60} alkynyl,
_{(Ix) C} 3 ~C ₆₀ cycloalkyl and _{(x) C} 2 ~C ₆₀ heteroaryl However, where the total number of carbon atoms in the carbon-containing group is less than 60,
Any hydrogen atom in any carbon-containing group selected from (iv), (v), (vi), (vii), (viii), (ix) and (x) is F, Cl, Br, I, CN, unsubstituted or halogenated alkyl, unsubstituted or halogenated (hetero) aryl, unsubstituted or halogenated (hetero) arylalkyl, unsubstituted or halogenated alkylsulfonyl, unsubstituted or halogenated (hetero) It may be substituted by a substituent independently selected from arylsulfonyl, unsubstituted or halogenated (hetero) arylalkylsulfonyl, unsubstituted or boron halide-containing hydrocarbon, unsubstituted or silicon halide-containing hydrocarbon. ;
n is a valence of a metal ion; and at least one of A ^{1 to} A ⁴ is F, CN, or an electron-withdrawing carbon group;
The electron-withdrawing carbon group is selected from hydrocarbons, boron-containing hydrocarbons, silicon-containing hydrocarbons and heteroaryls, wherein at least half of the hydrogen atoms have been replaced by F, Cl, Br, I and / or CN.

In one embodiment, M is selected from an alkali metal, an alkaline earth metal, a rare earth metal, a transition metal, or a transition metal excluding Ag, Al, Ga, In, Tl, Sn, Pb, Bi or a mixture thereof; n is 1, 2 or 3;
Preferably, M is selected from Li, Na, K, Rb, Cs, Cu or a mixture thereof, and n is 1;
Also preferably, M is selected from Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Cd or mixtures thereof, and n is 2;
More preferably, M is selected from Li, Na, Cu or a mixture thereof, and n is 1.
Still more preferably, M is selected from Mg, Ca, Mn, Zn, Cu or mixtures thereof, and n is 2.
Most preferably, M is Li and n is 1 or M is selected from Mg, Mn, Zn or a mixture thereof, and n is 2.

  In one embodiment, in the p-dopant molecule, the atom of the anion and / or the anionic ligand closest to the metal cation is a C atom or an N atom.

  In one embodiment, the acidity of the electrically neutral conjugate acid formed from said anion and / or anionic ligand by the addition of one or more protons in 1,2-dichloroethane is the acidity of HCl Higher, preferably higher than the acidity of HBr, more preferably higher than the acidity of HI, even more preferably higher than the acidity of fluorosulfuric acid, and most preferably higher than the acidity of perchloric acid .

  In one embodiment, the electrical p-dopant has a highest unoccupied orbital energy level calculated by standard quantum chemistry and the highest occupancy of the covalent hole transport compound calculated by standard quantum chemistry. Above the orbital energy level, at least 0.5 eV, preferably at least 0.6 eV, more preferably at least 0.8 eV, even more preferably at least 1.0 eV, most preferably at least 1.2 eV on an absolute vacuum scale. Show.

  The standard quantum chemistry method may be a software package TURBOMOLE using a DFT function B3LYP with a basis set def2-TZVP.

  In one embodiment, the first hole transport matrix compound has a highest occupied orbital energy level calculated by standard quantum chemistry and is less than -3.0 eV on an absolute vacuum scale, preferably -3. It exhibits less than 0.5 eV, more preferably less than -4.0 eV, even more preferably less than -4.5 eV, and most preferably less than -5.0 eV.

  In one embodiment, said first hole transport matrix compound is an organic compound, preferably an organic compound comprising a conjugated system of at least 6, more preferably at least 10, delocalized electrons, and preferably Wherein the first hole transport matrix compound comprises at least one triarylamine structural moiety, more preferably the first hole transport matrix compound comprises at least two triarylamine structural moieties.

  In one embodiment, within said first semiconductor layer, said p-dopant and said first hole transport matrix compound form two adjacent sub-layers.

In one embodiment, all the layers between the first electrode and the second electrode, as well as the electrode deposited on the last organic layer, have a pressure of less than 1 × 10 ⁻³ Pa, preferably It can be produced by vacuum deposition at a pressure of less than 5 × 10 ⁻⁴ Pa, more preferably a pressure of less than 1 × 10 ⁻⁴ Pa.

  The object is further achieved by a method for manufacturing a display device according to any of the above embodiments. The method includes at least one step wherein the hole transport matrix compound and the electrical p-dopant are exposed to and contiguous to a temperature of greater than 50C.

  "Intimate" should be understood to mean that both components are present in one condensed phase, or that they are present in two condensed phases that share a common phase interface.

In one embodiment, the method may include the following steps:
(I) dispersing the p-dopant and the first hole transport matrix compound in a solvent,
(Ii) depositing the dispersion on a substrate; and (iii) evaporating the solvent at a high temperature.

The method comprises the steps of: under reduced pressure, preferably a pressure of less than 1 × 10 ⁻² Pa and a temperature of more than 50 ° C., more preferably a pressure of less than 5 × 10 ⁻² Pa and a temperature of more than 80 ° C., even more preferably 1 × It may further comprise at least one step of evaporating said p-dopant at a pressure of less than 10 ⁻³ Pa and a temperature of more than 120 ° C., most preferably at a pressure of less than 5 × 10 ⁻⁴ Pa and a temperature of more than 150 ° C. .

  In one embodiment, the p-dopant may be used in the form of a solid hydrate.

  In another embodiment, the p-dopant may be used as an anhydrous solid comprising less than 0.10 wt% water, preferably less than 0.05 wt% water.

  Said object is further achieved by a compound having formula (Ia);

Wherein A ¹ is H;
A ² -A ⁴ are independently selected from perfluorinated indazolyl having formula (IIa) or (IIb):

Wherein the dashed bond represents the bond to the boron atom in formula (Ia)
R ¹ is a perfluorinated C ₁ -C ₂₀ hydrocarbon group,
M is Li and n is 1 or M is a divalent metal and n is 2.

  In one embodiment, the compound having the formula (Ia) is a solid compound.

In one embodiment, compounds where M is calcium and R ¹ is trifluoromethyl can be excluded.

  In one embodiment, the divalent metal M in the formula (Ia) is selected from Mg, Mn and Zn, and n is 2.

  Said object is further achieved by a compound having the formula (Iaa);

Wherein A ¹ is H;
A ^{2 to} A ⁴ are independently selected from perfluorinated indazolyl having formula (IIa) or (IIb)

Wherein the dashed bond represents the bond to the boron atom in formula (Ia),
R ¹ is a perfluorinated C ₁ -C ₂₀ hydrocarbon group,
M is Li and n is 1; or M is a divalent metal selected from Mg, Mn and Zn, and n is 2.

  Said object is further achieved by a compound having formula (Ib);

Wherein A ¹ is H and A ² -A ⁴ is independently selected from fluorinated pyrazolyl having formula (III):

Wherein the dashed bond represents the bond to the boron atom in formula (Ib), R ² and R ⁴ are independently selected from perfluorinated C ₁ -C ₂₀ hydrocarbon groups, and R ³ is H, selected from F, CN and perfluorinated _C 1 _{-C 20} hydrocarbon group;
M is Li and n is 1 or M is a divalent metal and n is 2.

In one embodiment, R ² and / or R ⁴ in formula (Ib) is trifluoromethyl.

  In one embodiment, the divalent metal M in the formula (Ib) is selected from Mg, Mn, and Zn, and n is 2.

  An important property of the materials included in organic semiconductor devices is their conductivity. As described in WO2016 / 050834, in a display device having a structured anode and at least two pixels sharing at least one hole transport layer and / or hole injection layer, the shared layer Limited conductivity may favor low levels of unwanted electrical crosstalk in the display. On the other hand, if the conductivity of the shared layer is too low, the operating voltage of the display may increase. WO 2016/050834 teaches a conductivity range that represents a compromise between these conflicting requirements.

  However, the authors of the present application surprisingly found that the electrical p-dopant based on certain metal salts and metal complexes, under certain conditions, has a level corresponding to the conductivity observed in a pure matrix. P-doped materials and / or p-doped materials that provide stable hole injection from state-of-the-art anodes into state-of-the-art hole transport matrices without substantially increasing the concentration of free charge carriers beyond It has been found that it is possible to produce doped layers.

This surprising finding is that even if it has a conductivity less than the optimal range between 1 × 10 ⁻⁵ S · m ^{−1 and} 1 × 10 ⁻⁶ S · m ⁻¹ disclosed in WO 2016/05083, This provided the opportunity to build a WO2016 / 050834 display operating at comparable voltages. The dopant of the present application is a display device of WO 2016/050834 with a level of electrical conductivity in a p-doped layer shared by a large number of pixels which is near or below the detection limit of available measuring means. Enables efficient operation of Thus, the dopants of the present application allow for further suppression of electrical crosstalk in OLED displays and also provide new opportunities for designing efficient OLED displays that exhibit very low levels of electrical crosstalk. I do. These observations made by the authors are described in further detail.

  In an earlier application EP 15181385 filed by the present applicant, several of the authors describe the successful use of some metal amides as shown below as hole injection materials in organic electrical devices.

  In parallel with the further investigation of similar metal amide compounds, the authors surprisingly found that some structurally distinct compounds, namely metal borate complexes such as I also found something.

  Most surprisingly, the authors point out that all of these structurally different compounds have two different modes in their p-doping behavior, depending on the doped materials and / or the process conditions during the production of the layers. Are similarly shown.

  In the first mode, semiconductor materials and / or layers doped with these compounds (which can be generalized as electrically neutral metal complexes with metal salts and / or anionic ligands) It exhibits a slightly lower, but well-measurable electrical conductivity as compared to materials and / or layers doped with typical redox p-dopants. This mode is likely to occur when the doped material and / or layer, even in trace amounts, is exposed to oxygen.

  In the second mode, semiconductor materials and / or layers doped with an electrically neutral metal complex containing the disclosed metal salts and / or anionic ligands exhibit almost measurable electrical conductivity. Absent. This mode occurs when contact of oxygen to the doped material and / or layer is strictly avoided throughout the process. The authors note that despite the very low conductivity of the materials and / or layers doped in the second manner, devices comprising such materials and / or layers, especially as hole transport or hole injection layers, are And still exhibit electrical behavior corresponding to excellent hole injection.

  The presence of the two modes of p-doping is advantageous for p-dopants of the present disclosure in organic electronic devices, particularly in displays that include a structured anode in multiple pixels that share a common hole transport layer. Provides inherent versatility in the use of. The conductivity of the common p-doped layer may be set to the limits taught in WO 2016/050834 by utilizing the first doping mode, or these limits may be utilized using the second doping mode. Can be set to less than.

  Furthermore, recent work done by the authors has shown that the materials and / or layers doped with the proposed metal salts and / or metal complexes are particularly suitable for materials provided according to the second mode of p-doping. Provided a clue that it may exhibit favorable thermal stability. In addition, these properties may be particularly suitable for use of the disclosed p-dopants in AMOLED displays. Because such displays must be structured into separate pixels, often require heat treatment of the p-doped layer or inevitable heating of the pre-deposited p-doped layer Because it requires the use of another process that may result in

  In certain embodiments of the present invention, the authors provide novel borate compounds comprising certain heterocyclic ligands wherein at least half of the hydrogen atoms have been replaced with an electron withdrawing group such as a halogen atom or a nitrile group. Offered. While LiTFSI and similar TFSI salts tend to deliquesce, the borate complex is substantially non-hygroscopic, in addition to the p-doping effect well comparable to the metal salts and / or anionic metal complexes of EP 15181385. And remains solid even at high air humidity.

Detailed description of the invention

  The conductivity of the thin layer sample can be measured, for example, by a so-called two-point method. At this time, a voltage is applied to the thin layer and the current flowing through said layer is measured. Resistance and conductivity are each obtained by considering the contact geometry and the thickness of the sample layer. The experimental set-up for conductivity measurements used by the authors of the present application is that the deposition of the p-doped layer as well as the conductivity of the p-doped layer under controlled conditions, especially with respect to contact of the deposited layer with air containing oxygen Enables rate measurement. In this regard, the entire series of deposition-measurements may be performed using solution processing techniques in a glove box or chamber containing controlled air, or may be performed in a fully evacuated chamber in a second chamber. It may be implemented using vacuum thermal evaporation (VTE), which may be selected as a particularly suitable method when materials and / or layers doped in a manner are required.

  In one embodiment, the electronic device may be an AMOLED display including a plurality of pixels including at least two pixels, wherein the first hole transport layer including a p-dopant is structured with a structured anode and a structured anode. It is arranged between the light emitting layer. In this embodiment, the first hole transport layer is shared by a plurality of pixels, where the lowest possible conductivity of the shared layer means that the electrical cross-connection between individual pixels operating at different voltages. To limit talk, it can be advantageous.

Here, the conductivity of the first hole transport layer is less than 1 × 10 ⁻⁶ S · m ⁻¹ , preferably less than 1 × 10 ⁻⁷ S · m ⁻¹ , more preferably 1 × 10 ⁻⁸ S · m ^{−1. -It} may be less than m- ¹ . When the detection limit of the used conductivity measurement method is less than 1 × 10 ⁻⁶ S · m ⁻¹ , in the electronic device of this embodiment, the conductivity of the first hole transport layer is less than the detection limit. Preferably, there is.

  In an AMOLED display, the cathode may be formed as a common cathode for multiple pixels. The common cathode can extend across all of the pixels in the OLED display. Conversely, every individual pixel can have its own anode that does not have to contact the anode of other individual pixels.

  Optionally, for one or more of the plurality of OLED pixels, the following organic layers can be provided: a hole blocking layer, an electron injection layer, and / or an electron blocking layer.

  In addition, the AMOLED display has a driving circuit configured to separately drive each of a plurality of pixels provided in the OLED display. In one embodiment, separately driving can include separate control of drive current applied to individual pixels.

  The first HTL is made from a hole transport matrix (HTM) material that is electrically doped with a p-dopant. The hole transport matrix material may be electrically doped with more than one p-dopant. Although the HTM material may consist of one or more HTM compounds, the term hole transport material is used throughout this application to refer to all semiconductor materials that include at least one hole transport matrix compound. Please understand that this is a broad term. The hole transport matrix material is not particularly limited. Generally, the hole transport matrix material is any material consisting of covalently bonded atoms that can embed a p-dopant. In this regard, predominantly covalent inorganic infinite crystals, such as silicon or germanium, or highly crosslinked inorganic glasses, such as silicate glasses, do not fall within the definition of a hole transport matrix material. Preferably, the hole transport matrix material may consist of one or more organic compounds.

  In an electronic device, the thickness of the first hole transport layer can be less than 150 nm, less than 100 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, or less than 15 nm.

  The thickness of the first hole transport layer can be greater than 3 nm, greater than 5 nm, greater than 8 nm, or greater than 10 nm.

  The anode may be made from a transparent conductive oxide (TCO) such as indium tin oxide (ITO) or aluminum zinc oxide (AZO). Alternatively, the anode may be made from one or more thin metal layers that result in a translucent anode. In another embodiment, the anode may be made from a thick metal layer that is not transparent to visible light.

  The electronic device may include an electron blocking layer (EBL) provided between the first hole transport layer and the light emitting layer. The EBL may be in direct contact with the first HTL and the EML. The electron blocking layer may be an undoped layer made from an organic hole transport matrix material (in other words, the electronic element layer does not contain an electrical dopant). The composition of the organic hole transport matrix material of the first hole transport layer may be the same as the composition of the organic hole transport matrix material of the electron blocking layer. In another embodiment of the present invention, the composition of both hole transport matrix materials may be different.

  The layer thickness of the EBL can be greater than 30 nm, greater than 50 nm, greater than 70 nm, greater than 100 nm, or greater than 110 nm.

  The thickness of the EBL can be less than 200 nm, less than 170 nm, less than 140 nm, or less than 130 nm. Compared to EBL, the common HTL may be about one step thinner.

  Each compound that forms the electron blocking layer can have a HOMO energy level that is higher than the highest occupied orbital (HOMO) level of any compound that forms the hole transport matrix material of the common hole transport layer. . The HOMO energy level is expressed on an absolute scale as compared with the case where the vacuum energy level is zero.

  The organic matrix material of the electron blocking layer can have a hole mobility greater than or equal to the hole mobility of the matrix material of the hole transport layer.

  The common HTL and / or EBL hole transport matrix (HTM) material can be selected from compounds comprising a conjugated system of delocalized electrons, wherein the conjugated system comprises at least two tertiary amine nitrogen atoms Lone electron pairs.

  Suitable compounds for the hole transport matrix material of the doped hole transport layer and / or the common hole transport layer can be selected from known hole transport matrices (HTM), such as triarylamine compounds. The HTM for the doped hole transport material may be a compound comprising a conjugated system of delocalized electrons, said conjugated system comprising a lone pair of at least two tertiary amine nitrogen atoms. For example, N4, N4′-di (naphthalen-1-yl) -N4, N4′-diphenyl- [1,1′-biphenyl] -4,4′-diamine (HT1), and N4, N4, N4 ″ , N4 ″ -tetra ([1,1′-biphenyl] -4-yl)-[1,1 ′: 4 ′, 1 ″ -terphenyl] -4,4 ″ -diamine (HT4). . The synthesis of terphenyldiamine HTM is described, for example, in WO2011 / 134458A1, US2012 / 223296A1 or WO2013 / 135237A1; the 1,3-phenylenediamine matrix is described, for example, in WO2014 / 060526A1. These documents are incorporated herein by reference. Many triarylamine HTMs are commercially available.

  The electronic device may further include a light absorbing layer disposed between the first electrode and the second electrode, for example, in a solar cell. In another embodiment, the electronic device may be an electroluminescent device comprising at least one light emitting layer between a first electrode and a second electrode.

  The light-emitting layer of an electroluminescent device may be continuous or structured. An example of an electroluminescent device that includes a structured emissive layer may include an AMOLED display that may include a plurality of sub-regions, each of which is assigned to one of a plurality of pixels. Preferably, the light emitting layer of each pixel corresponding to the sub-region of the light emitting layer of the display does not contact the light emitting layer of an adjacent pixel. In the display manufacturing process, the organic layer containing the EML of individual pixels is provided by fine metal masks (FMMs), laser-excited thermal transfer (LITI), and either in top-emitting, bottom-emitting, or bottom-emitting microcavities, for example. And / or can be patterned by known methods such as inkjet printing (IJP) (eg, Chung et al. (2006), 70.1: Invited Paper: Large-Sized Full Color AMOLED TV: Advancements and Issues. SID Symposium Digest of Technical Papers, 37: 1958-1963.doi: 10.1889 / 1.2451418; Lee et al. (2009), 53.4: Development of 31-Inch Full-HD AMOLED TV Using LTPS-TFT and RGB FMM.SID Symposium Digest of Technical Papers, 40 : 802-804. Doi: See 10.1889 / 1.3256911). RGB positioning may be provided.

  For a plurality of OLED pixels, a common electron transport layer may be formed by an electron transport layer provided in a stack of organic layers of the plurality of OLED pixels.

  The electron transport layer of the electronic device can include an organic electron transport matrix (ETM) material. Further, the electron transport layer may include one or more n-dopants. The compound suitable for ETM is not particularly limited. In one embodiment, the electron transport matrix compound comprises a covalent atom. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10, delocalized electrons. In one embodiment, a conjugated system of delocalized electrons may be included in the aromatic or heteroaromatic structural part, for example, as disclosed in the documents EP1970371A1 or WO2013 / 0721717A1.

  The cathode can be made from a metal or metal alloy having a low work function. Transparent cathodes made from TCO are also well known in the art.

  The stack of organic layers can be made from an organic compound having a molecular weight of less than 2000 g / mol. In yet another embodiment, the organic compound may have a molecular weight of less than 1000 g / mol.

In the following, further embodiments will be described in more detail by way of examples with reference to the drawings. In the drawings, the following are shown.
1 is a schematic diagram of an active OLED display, where the display has a plurality of OLED pixels.

  FIG. 1 shows a schematic diagram of an active OLED display 1 having a plurality of OLED pixels 2, 3, 4 provided in the OLED display 1. In the OLED display 1, each pixel 2, 3, 4 is provided with anodes 2a, 3a, 4a connected to a drive circuit (not shown). Various devices that can function as drive circuits for active matrix displays are known in the art. In one embodiment, the anodes 2a, 3a, 4a are made from TCO, for example ITO.

  Cathode 6 is assigned to electrically doped hole transport layer (HTL) 7, electron blocking layer (EBL) 5, pixels 2, 3, 4 and is provided separately in electron transport layer (ETL) 9. It is provided on the organic laminate including the light emitting layer (EML) having the sub-regions 2b, 3b, 4b. For example, sub-regions 2b, 3b, 4b can provide RGB combinations (R-red, G-green, B-blue) for a color display. By applying individual drive currents to the pixels 2, 3, 4 via the anodes 2a, 3a, 4a and the cathode 6, the display pixels 2, 3, 4 are operated independently.

(Synthesis Example)
<Lithium tris (4,5,6,7-tetrafluoro-3- (trifluoromethyl) -1H-indazol-1-yl) hydroborate (PB-1)>
[Step 1: 4,5,6,7-tetrafluoro-3- (trifluoromethyl) -1H-indazole]

Dissolve 11.09 g (45.1 mmol) of perfluoroacetophenone in 100 mL of toluene. The solution is cooled in an ice bath and 2.3 mL (2.37 g, 47.3 mmol, 1.05 equiv) of hydrazine monohydrate are added dropwise. The mixture is heated at reflux for 3 days. After cooling to room temperature, the mixture is washed twice with 100 mL of saturated aqueous sodium hydrogen carbonate solution and twice with 100 mL of water, dried over magnesium sulfate and the solvent is removed under reduced pressure. The yellow oily residue is bulb to bulb distilled at a temperature of about 140 ° C. and a pressure of about 12 Pa. Dissolve the crude product in hot hexane and store the solution at -18 ° C. The precipitated solid is filtered off and the suspension is washed twice with 10 mL of hexane. 5.0 g (43%) of the product was obtained as a slightly yellow solid.
GCMS: Expected M / z (mass / charge) ratio 258 confirmed.

  [Step 2: lithium tris (4,5,6,7-tetrafluoro-3- (trifluoromethyl) -1H-indazol-1-yl) hydroborate]

  Under Ar countercurrent, 5.1 g (19.8 mmol) of 4,5,6,7-tetrafluoro-3- (trifluoromethyl) -1H-indazole was added to the out-baked Schlenk flask. And treat with 3 mL of toluene. Freshly ground lithium borohydride is added to the starting material. The mixture is heated to 100 ° C. until hydrogen formation has ceased (about 4 hours). After cooling slightly, 15 mL of hexane is added and the mixture is heated at reflux for 10 minutes and cooled to room temperature. The precipitated solid is filtered off, washed with 10 ml of hot hexane and dried in a high vacuum. 2.55 g (49%) of the product were obtained as an off-white solid.

  <Lithium tris (3,5-bis (trifluoromethyl) -1H-pyrazol-1-yl) hydroborate (PB-2)>

  In the baked Schlenk flask, 2.0 g (9.8 mmol, 5 equivalents) of 3,5-bis (trifluoromethyl) pyrazole is dissolved in 5 mL of dry toluene. Under countercurrent of Ar, 43 mg (1.96 mmol, 1 eq) of freshly ground lithium borohydride are added and the mixture is heated to reflux for 3 days. The solvent and excess starting material are removed by distillation under reduced pressure and the residue is crystallized from n-chlorohexane. 0.25 g (20%) of the product was obtained as a white solid.

<Lithium tris (4,5,6,7-tetrafluoro-3- (perfluorophenyl) -1H-indazol-1-yl) hydroborate (PB-3)>
[Step 1: 4,5,6,7-tetrafluoro-3- (perfluorophenyl) -1H-indazole]

20.0 g (54.8 mmol) of perfluorobenzophenone are dissolved in 200 mL of toluene. 4.0 mL (4.11 g, 82.1 mmol, about 1.5 equiv) of hydrazine monohydrate are added dropwise to the ice-cooled solution. 40 g of sodium sulfate are added and the mixture is heated at reflux for 2 days. After cooling, 10 mL of acetone is added to the reaction mixture and the resulting suspension is stirred at room temperature for 1 hour. The solid is filtered off, washed thoroughly with 4 × 50 mL of toluene, the combined organic fractions are washed twice with saturated aqueous sodium bicarbonate. The solvent was removed under reduced pressure and the residue was purified by column chromatography. 7.92 g (41%) of the product was obtained as a pale yellow solid.
GC-MS: The expected M / z (mass / charge) ratio of 356 was confirmed.

  [Step 2: lithium tris (4,5,6,7-tetrafluoro-3- (perfluorophenyl) -1H-indazol-1-yl) hydroborate]

  In the baked Schlenk flask, 1.02 g (2.86 mmol, 3.0 equivalents) of 4,5,6,7-tetrafluoro-3- (perfluorophenyl) -1H-indazole was dissolved in 5 mL of chlorobenzene. Let it. Under countercurrent Ar, freshly ground lithium borohydride (21 mg, 0.95 mmol, 1.0 equiv) is added. The mixture is heated at 150 ° C. for 2 days and cooled to room temperature. The solvent is removed under reduced pressure and the residue is dried under high vacuum. The crude product is further purified by drying in a bulb-to-bulb still at a temperature of about 150 ° C. and a pressure of about 12 Pa. 0.57 g (70%) of the product was obtained as an off-white solid.

  <Lithium tris (3-cyano-5,6-difluoro-1H-indazol-1-yl) hydroborate (PB-4)>

  Freshly ground lithium borohydride (15 mg, 0.7 mmol, 1.0 eq.) Was placed in the baked pressure tube and 0.5 g (2.79 mmol, 4.0 eq.) Of 5, under countercurrent Ar. Add 6-difluoro-1H-indazole-3-carbonitrile and wash with 1 mL of toluene. Close the pressure tube and heat to a temperature of about 160 ° C. for about 21 hours. After cooling to room temperature, the mixture is treated with 5 mL of hexane in an ultrasonic bath for about 30 minutes. The precipitated solid is filtered off and washed with hexane (20 mL total). After drying, 0.48 g of a yellowish solid was obtained.

  <Zinc (II) tris (3,5-bis (trifluoromethyl) -1H-pyrazol-1-yl) hydroborate (PB-5)>

  Dissolve 0.57 g (0.91 mmol) lithium tris (3,5-bis (trifluoromethyl) -1H-pyrazol-1-yl) hydroborate in 6 mL N, N-dimethylformamide. An aqueous solution containing 62 mg of zinc dichloride in 1 mL of water is added dropwise. An additional 20 mL of water is added and the mixture is treated in an ultrasonic bath for 2 hours. The precipitate is filtered off and dried in a high vacuum. 0.485 g (82%) of the product was obtained as a white solid.

(Example of device)
<Device Example 1> (Bottom-emitting white OLED pixel type tandem OLED)
On a glass substrate with a 90 nm thick ITO anode, a 10 nm hole injection layer made of F1 doped with 8% by weight of PD-2 and a 140 nm thick undoped positive electrode made of pure F1. A hole transport layer, a 20 nm thick first emissive layer formed from ABH113 doped with 3% by weight BD200 (both provided by SFC, Korea), and a thickness made from pure F2 A first electron transport layer having a thickness of 25 nm, an electron generation portion (n-CGL) of a charge generation layer having a thickness of 10 nm made of F3 doped with 5% by weight of Yb, and a thickness made of F4 A 2 nm intermediate layer, a 30 nm thick charge generation layer made of PB-1 (p-CGL), and a 10 nm thick second hole transport layer made of pure F1 And the same thickness as the first light emitting layer And a 20 nm thick second electron-emitting layer made of pure F2 and a 10 nm thick electron made of F3 doped with 5% by weight of Yb. An injection layer (EIL) and a 100 nm Al cathode were sequentially deposited.

  All layers were deposited by vacuum thermal evaporation (VTE).

At a current density of 10 mA / cm ² , the operating voltage of the device at 8 V and the observed luminance were well comparable to the same device containing a commercially available state-of-the-art p-dopant instead of PB-1. In this preliminary experiment, the exact test required for efficiency evaluation was omitted.

<Device Example 2> (Bottom-emitting blue OLED pixel)
Next, the following layers were sequentially deposited by VTE on a glass substrate with the same ITO anode as in device example 1: 10 nm hole injection layer made from compound PB-1; made from pure F1. HTL with a thickness of 120 nm; 20 nm EML made from ABH113 doped with 3 wt% NUBD370 (both supplied by SFC, Korea); made from F2 doped with 50 wt% LiQ. 36 nm EIL / ETL; 100 nm Al cathode.

  The comparative device included HIL made from compound CN-HAT (CAS 105598-27-4) instead of PB-1.

The device of the present invention achieved a current density of 15 mA / cm ² and an EQE of 5.4% at a voltage of 5.2 V. On the other hand, the comparative device ran at 5.4V with 4.9% EQE.

<Equipment Example 3> (Device including homogeneous injection layer composed of hole transport matrix doped with borate complex)
The following layers were sequentially deposited by VTE on a glass substrate with the same ITO anode as in device example 2: 10 nm hole injection layer made of 8% by weight of matrix compound F2 doped with 5PB-1. 120 nm thick HTL made from pure F1; 20 nm EML made from 3 wt% NUBD370 doped ABH113 (both supplied by SFC, Korea); 50 wt% LiQ 36 nm EIL / ETL made from doped F2; 100 nm Al cathode.

The device of the present invention achieved a current density of 15 mA / cm ² and an EQE of 5.6% at a voltage of 5.6 V. LT97 (operating time required for the illuminance to decrease to 97% of the initial value at a current density of 15 mA / cm ² ) was 135 hours.

<Apparatus Example 4> (Tandem device including a homogeneous charge generation layer composed of a hole transport matrix doped with a borate complex)
In a device manufactured as in Example 1, the pure PB-1 layer was replaced by a layer of the same thickness consisting of F2 doped with 35% by weight of PB-1.

  The features disclosed in the foregoing description and in the dependent claims, both separately and in any combination thereof, may be the material for implementing the disclosed aspects made in the independent claims in its various forms.

Key symbols and abbreviations used throughout this specification:
CV cyclic voltammetry DSC differential scanning calorimetry EBL electron blocking layer EIL electron injection layer EML light emitting layer eq. Equivalent ETL electron transport layer ETM electron transport matrix Fc ferrocene Fc ⁺ ferricenium HBL hole blocking layer HIL hole injection layer HOMO highest occupied orbital HPLC high performance liquid chromatography HTL hole transport layer p-HTL p-doped hole transport Layer HTM hole transport matrix ITO indium tin oxide LUMO lowest unoccupied orbital mol% mol% NMR nuclear magnetic resonance OLED organic light emitting diode OPV organic photovoltaic QE quantum efficiency _Rf TLC delay factor RGB red-green-blue TCO transparent conductivity Oxide TFT thin film transistor _Tg glass transition temperature TLC thin layer chromatography wt% weight percent

Claims (18)

Including at least one first semiconductor layer between the first electrode and the second electrode;
Wherein the first semiconductor layer comprises:
(I) at least one first hole transport matrix compound comprising a covalent bond atom, and (ii) at least one electric p-dopant selected from a metal borate complex, wherein the metal borate salt An electrical p-dopant comprising at least one metal cation and at least one anionic ligand, said anionic ligand consisting of at least six covalently bonded atoms including at least one boron atom;
Including
An electronic device in which the first semiconductor layer is a hole injection layer, a hole injection section of a charge generation layer, or a hole transport layer. Further comprising at least one light emitting layer or at least one light absorbing layer between the first electrode and the second electrode;
The first electrode is an anode,
The electronic device according to claim 1, wherein the first semiconductor layer is disposed between the anode and the light emitting layer or between the anode and the light absorbing layer.   3. The electronic device according to claim 2, wherein the first semiconductor layer is adjacent to the anode.   The anionic ligand has at least 7, preferably at least 8, more preferably at least 9, even more preferably at least 10, even more preferably at least 11, and most preferably at least 12 covalent bonds The electronic device according to any one of claims 1 to 3, comprising an atom. The metal borate complex has the formula (I):

Wherein M is a metal ion;
A ¹ -A ⁴ are each independently selected from the following (i) to (x);
(I) H,
(Ii) F,
(Iii) CN,
_{(Iv) C} 6 ~C ₆₀ aryl,
_{(V) C} 7 ~C ₆₀ arylalkyl,
_{(Vi) C} 1 ~C ₆₀ alkyl,
_{(Vii) C} 2 ~C ₆₀ alkenyl,
_(Viii) C _{2 ~ 60} alkynyl,
_{(Ix) C} 3 ~C ₆₀ cycloalkyl and _{(x) C} 2 ~C ₆₀ heteroaryl However, where the total number of carbon atoms in the carbon-containing group is less than 60,
Any hydrogen atom in any carbon-containing group selected from (iv), (v), (vi), (vii), (viii), (ix) and (x) is F, Cl, Br, I, CN, unsubstituted or halogenated alkyl, unsubstituted or halogenated (hetero) aryl, unsubstituted or halogenated (hetero) arylalkyl, unsubstituted or halogenated alkylsulfonyl, unsubstituted or halogenated (hetero) It may be substituted by a substituent independently selected from arylsulfonyl, unsubstituted or halogenated (hetero) arylalkylsulfonyl, unsubstituted or boron halide-containing hydrocarbon, unsubstituted or silicon halide-containing hydrocarbon. ;
n is a valence of a metal ion; and at least one of A ^{1 to} A ⁴ is F, CN, or an electron-withdrawing carbon group;
The electron-withdrawing carbon group is selected from a hydrocarbon, a boron-containing hydrocarbon, a silicon-containing hydrocarbon, and a heteroaryl, wherein at least half of the hydrogen atoms have been replaced with F, Cl, Br, I, and / or CN; The electronic device according to claim 1. M is selected from alkali metals, alkaline earth metals, rare earth metals, transition metals (excluding silver, Al, Ga, In, Tl, Sn, Pb, Bi or mixtures thereof), and n is 1, 2 or 3 Is;
Preferably, M is selected from Li, Na, K, Rb, Cs, Cu or a mixture thereof, and n is 1;
Also preferably, M is selected from Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Cd or mixtures thereof, and n is 2;
More preferably, M is selected from Li, Na, Cu or a mixture thereof, and n is 1.
Still more preferably, M is selected from Mg, Ca, Mn, Zn, Cu or mixtures thereof, and n is 2.
Most preferably, M is Li and n is 1 or M is selected from Mg, Mn, Zn or a mixture thereof, and n is 2. Electronic device.   The electrical p-dopant has an energy level of the lowest unoccupied orbital calculated by standard quantum chemistry, and an energy level of the highest occupied orbital of the first hole transport compound calculated by standard quantum chemistry. At least 0.5 eV, preferably at least 0.6 eV, more preferably at least 0.8 eV, even more preferably at least 1.0 eV, most preferably at least 1.2 eV on an absolute vacuum scale. The electronic device according to any one of claims 1 to 6.   The first hole transport matrix compound has an energy level of the highest occupied orbital calculated by standard quantum chemistry and is less than -3.0 eV on an absolute vacuum scale, preferably less than -3.5 eV, and more The electronic device according to any one of claims 1 to 7, preferably exhibiting less than -4.0 eV, even more preferably less than -4.5 eV, most preferably less than -5.0 eV.   9. The electronic device according to claim 1, wherein in the first semiconductor layer, the p-dopant and the first hole transport matrix compound form two adjacent sub-layers. 10.   The first hole transport matrix compound is an organic compound, preferably an organic compound containing a conjugated system of at least 6, and preferably at least 10, delocalized electrons, and preferably the hole transport matrix compound. The matrix compound according to any one of claims 1 to 9, wherein the matrix compound comprises at least one triarylamine structural moiety, more preferably the compound is an organic compound comprising at least two triarylamine structural moieties. Electronic devices. All the layers between the first electrode and said second electrode, as well as the electrode deposited on the last organic layer, have a pressure of less than 1 × 10 ⁻³ Pa, preferably 5 × 10 ⁻⁴ Pa The electronic device according to any one of claims 1 to 10, which can be manufactured by vacuum deposition at a pressure of less than 1 Pa, more preferably a pressure of less than 1 x ^10-4 Pa.   The electron of claim 1, wherein the first hole transport matrix compound and the electrical p-dopant are exposed at a temperature greater than 50 ° C. and include at least one contiguous step. Device manufacturing method. Under reduced pressure, preferably a pressure of less than 1 × 10 ⁻² Pa and a temperature of more than 50 ° C., more preferably a pressure of less than 5 × 10 ⁻² Pa and a temperature of more than 80 ° C., even more preferably 1 × 10 ⁻³ Pa 13. The method of claim 12, further comprising evaporating the p-dopant at a pressure of less than 120C and a temperature of more than 120C, most preferably a pressure of less than ^5x10-4 Pa and a temperature of more than 150C. A compound having formula (Ia);

Wherein A ¹ is H;
A ² -A ⁴ are independently selected from perfluorinated indazolyl having formula (IIa) or (IIb):

Wherein the dashed bond represents the bond to the boron atom in formula (Ia)
R ¹ is a perfluorinated C ₁ -C ₂₀ hydrocarbon group,
M is Li and n is 1 or M is a divalent metal and n is 2.   The compound according to claim 14, wherein the divalent metal M is selected from Mg, Mn and Zn, and n is 2. A compound having the formula (Ib);

Wherein A ¹ is H;
A ² -A ⁴ is independently selected from fluorinated pyrazolyl having formula (III):

Wherein the dashed bond represents the bond to the boron atom in formula (Ib),
R ² and R ⁴ are independently selected from perfluorinated C ₁ -C ₂₀ hydrocarbon groups;
R ³ is selected from H, F, CN and from perfluorinated C ₁ -C ₂₀ hydrocarbon groups;
M is Li and n is 1 or M is a divalent metal and n is 2. Wherein R ² and / or R ⁴ is trifluoromethyl A compound according to claim 16. The compound according to claim 16 or 17, wherein M is a divalent metal selected from Mg, Mn, and Zn, and n is 2.

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